Mono azo dyestuffs containing a pyridyl group

ABSTRACT

Water-insoluble monoazo dyestuffs of the formula : WHEREIN A is optionally substituted aryl, X is hydrogen, optionally substituted aryl or alkyl optionally substituted by hydroxy, alkoxy or acyloxy, and Y is -R, -OR or -NR1R2, R being optionally substituted alkyl or aryl, and R1 and R2 each independently being hydrogen or optionally substituted alkyl or aryl, and the use of the dyestuffs for coloring synthetic polyester textile materials.

United States Patent Berrie et al.

[54] MONO AZO DYESTUFFS CONTAINING A PYRIDYL GROUP [72] Inventors: Alistair Howard Berrie; Nigel Hughes,

both of Manchester, England Imperial Chemical Industries Limited, London, England [22] Filed: June 23,1969

[21] Appl.No.: 835,749

[73] Assignee:

UNITED STATES PATENTS 3,487,066 12/1969 Ritter et al ..260/156 [451 May 23,1972

Primary Examiner.loseph Rebold Assistant Examiner-Donald M. Papuga Attomey-Cushman, Darby & Cushman ABSTRACT Water-insoluble monoazo dyestuffs of the formula:

wherein A is optionally substituted aryl, X is hydrogen, optionally substituted aryl or alkyl optionally substituted by hydroxy, alkoxy or acyloxy, and Y is R, -OR or NR R R being optionally substituted alkyl or aryl, and R and R each independently being hydrogen or optionally substi tuted alkyl or aryl, and the use of the dyestuffs for colouring synthetic polyester textile materials.

2 Claims, No Drawings HO O wherein A is an optionally substituted aryl radical, Y is a -R, OR or -NRR radical, R is an optionally substituted alkyl or aryl radical, R and R each independently represent a hydrogen atom or an optionally substituted alkyl or aryl radical, or R and R together form with the nitrogen atom N a fiveor six-membered nitrogen containing heterocyclic ring, and X is a hydrogen atom, or an alkyl radical which is optionally substituted by a hydroxy, alkoxy or acyloxy group, or an optionally substituted aryl radical, provided that the dyestuffs are free from carboxylic acid and sulphonic acid groups.

The dyestuffs of the invention can exist in a number of possible tautomeric forms. For convenience the dyestuffs have been formulated in one of these forms, but it is to be understood that the specification relates to the dyestufis in any of the possible tautomeric forms.

As examples of the optionally substituted aryl radicals represented by A there may be mentioned optionally substituted naphthyl radicals and preferably optionally substituted phenyl radicals, in particular phenyl radicals substituted by one or more of the same or different substituents such as chlorine, bromine, nitro, cyano, lower alkyl such as methyl, lower alkoxy such as methoxy, trifluoromethyl, lower alkyl sulphonyl, lower alkyl carbonyl, carbo lower alkoxy such as carboethoxy and hydroxy and lower alkoxy derivatives thereof such as carbo-fi-hydroxyethoxy, carbo-B-methoxyethoxy and carbo-B-(B-ethoxy ethoxy)ethoxy, sulphonamido and N-lower alkyl and N:N-di(lower alkyl)derivatives thereof, sulphonanilido, carbonamido and N- lower alkyl and N:N-di(lower alkyl)derivatives thereof, sulphamato (-OSO Nl-l and N-lower alkyl and N:N-di( lower alkyl) derivatives thereof, phenyl, N:N-di(lower alkyl) amino and phthalyl (which combines to form an anthraquinone nucleus).

Throughout this Specification the terms lower alkyl and lower alkoxy are used to denote alkyl and alkoxy radicals respectively containing from one to four carbon atoms.

The optionally substituted alkyl radicals represented by R, R and R are preferably optionally substituted lower alkyl radicals; and as examples of the said radicals there may be mentioned lower alkyl such as methyl, ethyl, propyl and butyl, hydroxy lower alkyl such as B-hydroxyethyl, aryl lower alkyl such as benzyl and B-phenylethyl, and lower alkoxy lower alkyl such as B-(methoxy or ethoxy) ethyl. The optionally substituted aryl radicals represented by R, R, R and X are preferably optionally substituted phenyl radicals; such as phenyl itself and tolyl, anisyl, chlorophenyl, bromophenyl and dimethylphenyl.

The alkyl radicals represented by X which are optionally substituted by hydroxy, alkoxy or acyloxy groups are preferably lower alkyl radicals which may be substituted by the said groups; and as specific examples of such radicals represented by X there may be mentioned lower alkyl such as methyl, ethyl, propyl and butyl, hydroxy lower alkyl such as B- hydroxyethyl and B- or 'yhydroxypropyl, lower alkoxy lower alkyl such as B-(methoxy or ethoxy)ethyl and )8- or 'y- (methoxy or ethoxy)propyl, and acyloxy lower alkyl in particular lower alkylcarbonyloxy lower alkyl such as B-acetoxyethyl, B-propionyloxyethyl and acetoxymethyl.

As examples of the fiveand six-membered nitrogen-containing heterocyclic rings formed by joining R, R and the nitrogen atom together there may be mentioned morpholino, piperidino and pyrrolidino.

According to a further feature of the invention there is provided a process for the manufacture of the monoazo dyestuffs of the invention which comprises coupling a diazo compound of an amine of the formula A-NH with a coupling component of the formula Formula I wherein A, X and Y have the meanings stated above, the amine and the coupling component being free from carboxylic acid and sulphonic acid groups.

The process of the invention can be conveniently carried out by adding the diazo compound, which is generally in the form of a solution or suspension in an aqueous acidic medium, to a solution or suspension of the coupling component in water and/ or a water-miscible organic liquid optionally containing an inorganic acid or an alkali metal hydroxide or carbonate, if necessary adjusting the pH of the mixture to effect coupling, and thereafter isolating the dyestuff by conventional methods.

As examples of the amines of the formula A-NH there may be mentioned aniline, 0-, mor p-toluidine, o-, mor pchloroaniline, o-, mor p-bromoaniline, o-, mor pnitroaniline, 2:5-dichloroaniline, 2:4-dinitroaniline, 2:4- dinitro-fi-(chloro or bromo)aniline, 4-methanesulphonylaniline, 4-aminobenzotrifluoride, 4- or 5-nitro-2-toluidine, 4- or 5-nitro-2-anisidine, 4- or 5-chloro-2-anisidine, 4- or 5- chloro2-toluidine, 4- or 5-bromo-2-anisidine, 2:6-di(chloroor bromo-)-4-nitroaniline, 2:4:6-tri-nitroaniline, 2:4-dinitro-6- carbomethoxyaniline, Z-amino-S-nitrobenzotrifluoride, 2:4- bis(methanesulphonyl)aniline, 2-(chloroor bromo-)-4- nitroaniline, methylanthranilate, 4- or S-nitromethylanthranilate, B-hydroxyethyl 4-aminobenzoate, B-methoxyethyl 4- aminobenzoate, 4-aminobenzamide, 2:6-di (chloroor bromo- )-aniline-4-sulphonamide, 2:6-di(chloroor bromo-)-4- methyl-sulphonylaniline, 2:5-di(chloroor bromo-)-4:6- dinitroaniline, 2-amino-3:S-dinitrobenzotrifluoride, 3-amino- 2-(chloroor bromo-)-4:6 -dinitro-(toluene or anisole), 3- amino-4-(chloroor bromo-)-2:6-dinitro-(toluene or anisole), 2- or 4-cyano-aniline, 4-nitro2-cyanoaniline, 2:4-dinitro-6- cyanoaniline, 2-nitro-4'cyanoaniline, 2-chloro-4- cyanoaniline, 3-amino-224:6-trinitrotoluene, 2-(chloroor bromo-)-4-methylsulphonylaniline, 3-(chloroor bromo-)-4- thiocyanatoaniline, 2-(chloroor bromo-)-4-sulphamylaniline, Z-amino-S-nitrophenylmethanesulphone, 2-amino- 3:S-dinitrophenylmethylsulphone, 2-amino-3-(chloroor bromo-)-5-nitrophenylmethylsulphone, 2-sulphamyl-4- nitroaniline, 2-methylsulphamyl-4-nitroaniline, 2-ethylsulphamyl-4-nitroaniline, 2-butylsulphamyl-4-nitroaniline, 2- dimethylsulphamyl-4-nitroaniline, 2-methylsulphamyl-4z6- dinitroaniline, Z-methylsulphamyl-4-nitro-6-(chloroor bromo-)aniline, 2-phenylsulphamyl-4-nitroaniline, methyl 2- amino-3-(chloroor bromo-)-5-nitro-benzoate, dimethyl 2- aminoterephthalate, dimethyl 2-amino-6-nitroterephthalate, aniline 2, 3- or 4sulphamate, 2-, 3- or 4aminobenzene N:N- dimethylsulphamate, l-naphthylamine, lor 2- aminoanthraquinone and 4-aminodiphenyl.

The coupling components of Formula I can themselves be obtained by a variety of methods such as are described in, for example, Heterocyclic Compounds Pyridine and its Derivatives Part 3 edited by Klingsberg, which was published by lnterscience Publishers in 1962. For example by um alginate, into the aqueous dispersion of the said monoazo cyclization of amide, ester or nitrile derivatives of the apdyestufi. propriately azfi-disubstituted glutaconic acid. At the conclusion of the coloring process it is preferred to As specific examples of the said coupling components there give the colored textile material a rinse in water or a brief may be mentioned 2:6-dihydroxy-3-carbonamido-4-methyl 5 soaping treatment before finally drying the colored textile pyridine, 2:6-dihydroxy-3-carbethoxy-4-methyl pyridine, 2:6- material. In the case of aromatic polyester textile materials it dihydroxy-3-carbondiethylamido-4-methyl pyridine, 2:6- is also preferred to subject the colored textile material to a dihydroxy-3-carbonamido pyridine, 2:6-dihydroxy-3-cartreatment in an alkaline aqueous solution of sodium hydrosulbonamido-4-phenyl pyridine and 2:6-dihydroxy-3-carbethoxyphite before the soaping treatment in order to remove loosely 4- h idi attached dyestuff from the surface of the textile material.

One preferred class of the monoazo dyestuffs of the inven- The monoazo dyestuffs have excellent afiinity and building tion comprises the dyestuffs wherein A is an optionally subup properties on synthetic textile materials, and in particular stituted phenyl radical. on aromatic polyester textile materials, so enabling heavy A second preferred class of the monoazo dyestuffs of the invention comprises the monoazo dyestuffs of the formula depths of shade to be obtained. The resulting colorations which range in shade from yellow to violet, have excellent fastness to light, to wet treatments, and, in particular, to dry heat treatments such as those carried out at high temperatures X1 during pleating operations.

If desired the dyestuffs of the invention can be applied to synthetic textile materials in conjunction with other disperse dyes, such as are described in, for example, British Pat. 119 specifications Nos. 806271, 835819, 840903, 847175, 852493, 859899, 865328, 872204, 894012, 908656, 909843, 910306, 913856, 919424, 944513, 944722, 953887, 959816,

960235 and 961412.

The invention is illustrated but not limited by the following examples in which the parts are by weight. Example 1 3O 5 Parts of a 14 percent aqueous solution of sodium nitrate are added to a solution of 216 parts of 3-aminobenzene NzN- dimethyl sulpharnate in a mixture of 50 parts of water and 2.5 parts of a concentrated aqueous solution of hydrochloric acid, and the mixture is stirred for a further 15 minutes at the same temperature.

The resulting solution of the diazo compound is gradually wherein A is an optionally substituted phenyl radical, X is a lower alkyl radical and Y has the meaning stated. in particular the group -COY represents a carbo lower alkoxy or carbonamido radical.

The water-insoluble monoazo dyestufis of the invention are valuable for coloring synthetic textile materials, in particular cellulose acetate and cellulose triacetate textile materials, polyamide textile materials such as polyhexamethylene-adipamide textile materials, and preferably aromatic polyester textile materials such as polyethylene terephthalate textile materials. Such textile materials can be in the form of thread, added with i to a l i f 1 7 parts f zzo-dihydroxyyarn, wovfin 3-carbonamido-4-methylpyridine and 5 parts of sodium Such textile materials can conveniently be colored with the acetate in 110 parts ofa 08 percent aqueous somtion of sodi monoazo dyestufis, as hereinbefore defined, by immersing the 40 um hydroxide at C and the mixture is stirred for a textile material in a dyebath comprising an aqueous dispersion further 15 minutes The mixture is acidified with acetic acid, of One more of the Said dyestuffs, which dyebath Preferably and the precipitated dyestuff is filtered off, washed with water contains a non-ionic, cationic and/or anionic surface-active and dried agent, and thereafter heating the dyebath for a period at a w dispersed in aqueous medium the smobtained suitable temperature. in the case of secondary cellulose m dyes aromatic polyester textile materials in deep acetate textile materials it iS preferred {0 carry out the greenish.ye]]ow hades of excellent fasmess properties Process at a temperimu'fi between and C; in the Case The 2:G-dihydroxy-3-carbonamido-4-methylpyridine used of cellulose triacetate or polyamide textile material it is i h above example was it lf b i d b condensing preferred to carry o h dye g pro at t0 in malonodiamide with ethyl acetoacetate in the presence of the case of aromatic polyester textile materials the dyeing 50 di m id process can either be carried out at a temperature between The following table gives further examples of the monoazo 90 and 100 C. preferably in the presence of a carrier Su h s dyestufls of the invention which are obtained by diazotizing diphenyl or o-hydroxydiphenyl, or at a temperature above the amines listed in the second column of the table and 100 C., preferably at a temperature between and ,coupling the resulting diazo compounds with the coupling C., under superatmospheric pressure. 55 components listed in the third column of the table using Alternatively the aqueous dispersion of the said monoazo h d i il to h t de e bed i E l 1 The f rth dyestuff can be applied to the textile materi l by 8 pad ing 01' column of the table indicates the shades obtained when the printing process, followed by heating or steaming of the textile dyestuffs are applied to aromatic polyester textile materials. material. in such processes it is preferred to incorporate a The 2:-dihydroxy-3-carboethoxy-4-methylpyridine was thickening agent, such as gum tragacanth, gum arabic, or sodi- 60 obtained by reacting acetoacetamide with diethylmalonate in Example Amine Coupling component Shade 2 2chl0r0aniline 2 greenish yellow, 3 4-chloroaniline 4 2-nitruaniline, D0,

5 3-nltroaniline DO 2-an1sxd1ne. 4-toluidine Ethyl 4-aminobenzoate B-Methoxyethyl S-mninobenzoa l-naphthylamine Do. Reddish yellow.

Yello Greenish yellow.

l-aminoanthraquinone. Do. 4-aminodiphenyl Do.

Aniline Greenish yellow.

a-methyl-2-nitroani1ine. a a v Reddish yellow.

4-methoxy-2-nitroaniline. a A Orange.

4-cyanoaniline d A v Greel'llSl'l yellow.

2-chloro-4-nitroaniliner l D0. 4chloro-2nitroaniline V D0.

xample Amine Jillilltr-l-lilulliylpyridine Ethyl -i-aminobenzoate Vlnlr-L.

(in-mush yvllow.

(lrm-nish yellowv (lri-r-uish yellow.

0 2,G-dihydroxy-3-carboethoxy4- h nyl ridine Orange.

D 2.l-dichloronnilinou. Do. 2A.5-tricliloroaniline D0. 2-nil'ronnilinc Do. Ethyl 4aminohen7.oote. d

D0. 4methyl2-nitroaniline. d Red digh yellow. 4-trifluorom ethylanilino. 4-hromoaniline Do. incetylaxninoaniline 3-methylsulohonylaniline, nov 4-acetylnniline D0. Aniline-4-sulnhonnmide. Do. Aniline-4-snlnhon-Nethylmmde. D Aniline4-sulphonN,N-diethylamide D 4-aminobenzamido Dov 4-amino enzanilide 3-ominobenZ-N-ethylamide Do. 4-acetylaminoaniline Do. 4-methoxy-2-nitroanilie Orange. 4-chloroaniline. Yellow. imitroaniline Greenish yellow o Do. 73 Ethyl 4-amin Do.

the presence of sodium ethoxide. On transesterlficatron with wherein A is selected from the group consisting of phenyl, ,B-ethoxyethanol this gave 2:6-d1hydroxy-3-( carbo-B-ethoxnaphthyl and phenyl substituted with a member selected from y y)- y py eon treatment with ethylamine, the group consisting of chlorine, bromine, diethylamine, aniline, p-anisidine or piperidine, the 2:6- dihydroxy-3-carboethoxy-4-methylpyridine gave the corresponding 3-carbonamido compounds.

2:6-Dihydroxy-3-(acetyl or benzoyl)-4-methylpyridines were obtained by reacting 2:6-dihydroxy-4-methylpyridine with acetyl chloride or benzoyl chloride in the presence of aluminium chloride.

2z6-Dihydroxy-3-carboethoxy-4-(hydroxymethyl or methoxymethyl)pyridine were obtained by condensing 4- (hydroxy or methoxy)-3-oxobutanoic acid with diethylmalonate in the presence of sodium ethoxide.

2:6-Dihydroxy-3-carboethoxy-4-acetoxymethylpyridine was obtained by acetylating the corresponding 4-hydroxymethyl compound.

2:6-Dihydroxy-3-carboethoxy-4-(phenyl or p-chlorophenyl)pyridine were obtained by condensing benzoylacetamide or the corresponding p-chloro derivative with diethylmalonate in the presence of sodium ethoxide.

nitro, cyano, lower alkyl, lower alkoxy, acetylamino, trifluoromethyl, lower alkylsulphonyl, lower alkylcarbonyl, carbo lower alkoxy, carbo lower alkoxy lower alkoxy, carbo hydroxy lower alkoxy, sulphonamido, N-lower alkyl sulphonamido, NzN-di (lower alkyl) sulphonamido, N-phenylsulphonamido, N-carbonamido, N-lower alkylcarbonamido, NzN-di (lower alkyl) carbonamido, sulphamato, N-lower alkylsulphamato, N:N-di (lower alkyl) sulphamato, phenyl, NzN-di (lower alkyl) amino and phthalyl, X is selected from the group consisting of hydrogen, lower alkyl, hydroxy lower alkyl, lower alkoxy lower alkyl and lower alkyl carbonyloxy lower alkyl and Y is selected from the group consisting of -R, -OR and -NRR wherein R is selected from the group consisting of lower alkyl,

lower alkoxy lower alkyl, hydroxy lower alkyl, phenyl,

chlorophenyl and methoxyphenyl and R and R each independently are selected from the group consisting of hydrogen,

lower alkyl, phenyl and methoxy phenyl and R and R together with the nitrogen atom to which they are attached 2:6-Dihydroxy-3-( carbo-,B-hydroxyethoxy, carbophenoxy f the piperidine ring and carbo-p-chlorophenoxy)-4-methylpyridine were obtained The wate r-insoluble monoazo dyestuff of claim 1 having by trans-estenficauon of 2:6-dihydroxy-3carboethoxy-4- methylpyridine with ethylene glycol, phenol and pchlorophenol respectively.

We claim: 1. Water-insoluble monoazo dyestufi free from sulphonic acid and carboxylic acid groups having the general formula AN=N- 00y 65 the formula wherein A has the meaning given in claim 4, X'is lower alkyl 0 and -COY is selected from the group consisting of carbo lower alkoxy and carbonamido.

F ZZ

Greenish yellow.

A Greenish yellow. 

2. The water-insoluble monoazo dyestuff of claim 1 having the formula wherein A has the meaning given in claim 4, X1is lower alkyl and -COY is selected from the group consisting of carbo lower alkoxy and carbonamido. 